BRPI0708443A2 - polymeric compositions containing polymers obtained by reduced recycled color metathesis - Google Patents

Abstract

POLYMERIC COMPOSITIONS CONTAINING POLYMERS OBTAINED BY METATHESIS WITH REDUCED RECYCLED COLORS. The present invention relates to aromatic polyester compositions, such as PET, which comprises an unsaturated polymer prepared via polymerization by metathesis which has at least or more specified end functional groups.

Description

Report of the Invention Patent for "POLYMERIC COMPOSITIONS CONTAINING POLYMERS OBTAINED BY REDUCED RECYCLED COLOR".

Such patent application claims the benefit of provisional patent application No. U.S. 60 / 777,970 filed March 12, 2006, which is hereby incorporated in its entirety by reference.

The present invention relates to aromatic polyester compositions comprising unsaturated polymers prepared by polymerization via metastasis.

Background of the Invention

Polyester resins, such as poly (ethylene terephthalate) are commonly used to make containers that are useful in food and beverage packaging. These resins, however, have a limited packaging life, especially in the packaging of foods and beverages that are sensitive or degrade in the presence of oxygen.

To overcome these shortcomings, these resins were mixed or reacted with unsaturated polymers such as polybutadiene.

Unfortunately, the presence of such unsaturated polymers within the polyester composition results in difficulty in recycling. That is, such compositions are not desired for recycling due to color formation during the drying cycle. In particular, such compositions have undergone red and yellow discoloration.

Since the use of these materials remains desired, and the ability to recycle these materials is technologically important, there is a need to overcome problems associated with color formation within these materials.

In one or more embodiments, the present invention relates to a composition comprising the reaction product or a mixture of, (i) an aromatic polyester, and (ii) an unsaturated polymer having at least one terminal functional group, wherein said unsaturated polymer is formed by metathesis polymerization.

In one or more embodiments, the present invention also relates to a composition comprising the reaction, product, or mixture of (i) an aromatic polyester resin; and (U) an unsaturated polymer having at least one terminal functional group, wherein said unsaturated polymer is formed by metathesis polymerization.

The terminal functional group which is usable herein is a group selected from hydroxyl, carboxylic acid, ester, carbonate, cyclic carbonate, anhydride, cyclic anhydride, lactone, amine, amide, lactam, cyclic ether, ether, aldehyde, thiazoline, oxazoline , phenol, melamine, and mixtures thereof. In one embodiment, the terminal functional group is a group selected from hydroxyl, carboxylic acid, and ester, and mixtures thereof.

Detailed Description of Illustrative Modalities

The introduction

One or more embodiments of this invention relate to an aromatic polyester resin composition comprising an unsaturated metathesis polymer having at least one terminal functional group. In one or more embodiments, the unsaturated polymer is prepared by employing any metathesis reaction techniques. In one or more embodiments, the unsaturated metathesis opolymer is characterized by a vinyl pendant group content of less than about 2%. In these and other embodiments, the metathesis unsaturated polymer is characterized by having about 5 to about 25 double bonds per 100 carbon atoms in the polymer chain.

The terminal functional group which is usable herein is a group selected from hydroxyl, carboxylic acid, ester, carbonate, cyclic carbonate, anhydride, cyclic anhydride, lactone, amine, amide, lactam, cyclic ether, ether, aldehyde, thiazoline, oxazoline , phenol, melamine, and mixtures thereof. In one embodiment, the terminal functional group is a group selected from hydroxyl, carboxylic acid, and ester, and mixtures thereof.

B. Aromatic Polyester

1. Composition

In this invention, any polyester aromatic resin may be used. In one or more embodiments, aromatic polyester resins are derived from aromatic dicarboxylic acids and diols. Exemplary dicarboxylic acids include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl carboxylic acid diphenyl dicarboxylic acid, diphenyl dicarboxylic acid, diphenoxyethanedicarboxylic acid, and mixtures thereof. In one or more embodiments, the polyesters may be derived from derivatives of such acids, such as dimethyl esters thereof. Exemplary diols include ethylene glycol, trimethylene glycol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol, cyclohexanedimethanol, tricyclodecanedimethanol, 2,2-bis (4-hydroxy ethoxy phenyl) propane, 4,4'-bis (hydroxyethyl) diphenyl sulfone ), diethylene glycol and mixtures thereof.

Examples of aromatic polyesters which may be employed in one or more embodiments include poly (alkylene terephthalate) resins, such as poly (ethylene terephthalate), poly (butylene terephthalate), and poly (cyclohexanedimethylene terephthalate). Others include poly (alkylene naphthalate) resins, such as poly (ethylene naphthalate), poly (butylene naphthalate), and poly (cyclohexane dimethylene naphthalate).

2. Features

In one or more embodiments, the aromatic polyester resin may be characterized by an intrinsic viscosity that is above 0.5 dl / g, in other embodiments above 0.6 dl / g, and in other embodiments above 0 dl / g. 1.7 dl / g when intrinsic viscosity is measured at 25 ° C. A 50/50 mixture of phenol and 1,1,2,2-tetrachloroethane. In these and other embodiments, the aromatic polyester resin may be characterized by an intrinsic viscosity that is less than 1.2 dl / g, in other modalities less than 1.0 dl / g, and in other modalities less than 0.95 dl / g.

In one or more embodiments, the aromatic polyester resin may be characterized by a melt temperature which is above 200 ° C, in other embodiments above 220 ° C, and in other embodiments above 230 ° C.

3. Summary

In one or more embodiments, aromatic polyester resins include those prepared from dimethyl terephthalate and ethylene glycol by a two-stage esterification process. Others include those prepared by direct esterification of a diacid with a diol or esterification of the diacid with ethylene oxide. Other methods for producing desired resins for use in this invention are also known, such as those methods described in U.S. Patent No. 6,083,585, which is incorporated herein by reference. Unsaturated Metathesis Polymer1. General

The unsaturated polymers employed in the present invention are metathesis synthesized polymers having at least one or more terminal functional groups. In one or more embodiments, olefins, such as cycloolefins and alpha, omega dienes, are polymerized by employing a metathesis catalyst to form the unsaturated polymer. The reaction of metathesis can be ring opening metathesis polymerization (ROMP) or acyclic diene metathesis polymerization (ADMET), or the like. In certain embodiments, the high molecular weight polymers synthesized by metathesis are modified (e.g., molecular weight reduction) by employing metathesis catalysts to provide unsaturated polymers useful for practicing the present invention. A functional olefin (i.e. an olefin that includes one or more functional groups) is employed to produce unsaturated functional polymers or protected functional polymers. Unsaturated polymers comprise one or more functional groups. By employing metathesis polymerization techniques, the resulting polymer has from about 5 to about 25 double bonds per 100 carbon atoms in the polymer chain.

The terminal functional group which is usable herein is a group selected from hydroxyl, carboxylic acid, ester, carbonate, cyclic carbonate, anhydride, cyclic anhydride, lactone, amine, amide, lactam, cyclic ether, ether, aldehyde, thiazoline, oxazoline , phenol, melamine, and mixtures thereof. In one embodiment, the terminal functional group is a group selected from hydroxyl, carboxylic acid, and ester, and mixtures thereof. Catalyst

Many metathesis catalysts are useful for practicing this invention. In one or more embodiments, the metathesis catalyst includes carbene transition metal complex. Suitable transition metal carbon complexes include a positively charged metal center (e.g., in the +2, +4, or +6 oxidation state) that is penta or hexacoordinated. Exemplary transition metals include transition metals from Groups 3 to 12 of the Periodic Table according to the IUPAC conventions.

In one or more embodiments, the metathesis catalyst includes ruthenium-based or osmium-based metathesis catalyst. Any ruthenium or osmium based metathesis catalyst that is effective for metathesis polymerization reactions can be used. Advantageously, certain ruthenium and / or osmium based catalysts are unaffected or only immaterially affected by the presence of certain advantageous functional groups present in the alkene.

In one embodiment, the deruthenium or osmium-based metathesis catalysts include carbene complexes of the type sometimes referred to as Grubbs catalysts. Grubbs metathesis catalysts are described in US Patent Nos. 5,312,940, 5,342,909, 5,831,108.5,969,170, 6,111,121, 6,211,391, 6,624,265, and 6,696,597 and Published Patent Applications Nos. US 2003/0181609 A1, 2003/0236427 A1 and 2004 / 0097745A9, all of which are incorporated herein by reference.

Ru or Os-based metathesis catalysts include compounds which may be represented by the formula

<formula> formula see original document page 6 </formula>

where M includes ruthenium or os, each LeL 'independently includes any neutral electron donor, each AeA' independently includes an anionic substituent, R3 and R4 independently comprise hydrogen or an organic group, and include an integer from 0 to about 5, or where two or more of R3, R4, L, L ', A and A' combine to form a bidentate substituent.

In one embodiment, LeL 'independently include groups phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibnite, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, thioether, trizolidide, or imidazolidene, or L and L 'may together include a bidirectional ligand. In one embodiment, L and / or L 'include an imidizolidene group which may be represented by the formulas

<formula> formula see original document page 7 </formula>

wherein R5 and R6 independently include alkyl, aryl, or substituted aryls. In one embodiment, R5 and R6 independently include substituted phenols, and in another embodiment, R5 and R6 independently include mesityl. In one embodiment, R 7 and R 8 include alkyl or aryl, or form a cycloalkyl, and in another embodiment, both are hydrogen, grupost-butyl or phenyl. Two or more of R5, R6, R7 and R8 may combine to form a cyclic moiety. Examples of imidazolidine linkers include 4,5-dihydroimidazol-2-ylidene ligands.

In one embodiment, A and A 'independently include halogen, hydrogen, C1-C20 alkyl, aryl, C1-C20 alkoxide, aryloxide, C2-C20 alkoxycarbonyl, arylcarboxylate, C1-C20 carboxylate, arylsulfonyl, C1-C20 alkyl -sulfonyl, C1-C20 alkylsulfinyl, each binder optionally being substituted by C1-C5 alkyl, halogen, C1-C5 alkoxy, or a phenyl group which is optionally substituted by halogen, C1-C5 alkyl, or C1-C5 alkoxy-xi , and A and A 'together may optionally include a bidentate ligand.

In one embodiment, R3 and R4 include independently selected groups of hydrogen, C1-C20 alkyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, aryloxy, C1-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl, 1a and C 1 -C 20 alkylsulfinyl, each R 3 and R 4 being optionally substituted by C 1 -C 5 alkyl, halogen, C 1 -C 5 alkoxy or a phenyl group which is optionally substituted by halogen, C 1 -C 5 alkyl, or C 1 -C 5 alkoxy.

form one or more Bidentate Ligants. Examples of such complexes are described as Class II catalysts in U.S. Patent No. 6,696,597. In another embodiment, R 3 or R 4 and L or L 'or A or A' may combine to form one or more bidentate linkers. This type of complex is sometimes referred to as Hoveyda or Hoveyda-Grubbs catalysts. Examples of bidentate linkers which may be formed by R3 or R4 and L or L 'include ortho-alkoxyphenylmethylene binders.

Other useful catalysts include hexa-valent carbene compounds which include those represented by the formula

<formula> formula see original document page 8 </formula>

As with any neutral electron donor ligand, each A, A 'and A' independently includes an anionic substituent, and R3 and R4 independently comprise hydrogen or an organic group. Similarly to the pentavalent catalysts described above, one or more substituents. The hexavalent complex may combine to form a bi-dented substituent.

ruthenium, dichloro (phenylmethylene) bis (tricyclohexylphosphine), ruthenium, dichloro (phenylmethylene) bis (tricyclopentylphosphine), ruthenium, dichloro (3-methyl-2-butenylidene) bis (tricyclohexylphosphine), ruthenium, methylthio -2-butenylidene) bis (tricyclopentylphosphine), ruthenium, dichloro (3-phenyl-2-propenylidene) bis (tricyclohexylphosphine), ruthenium, dichloro-ro (3-phenyl-2-propenylidene) bis (tricyclopentylphosphine), ruthenium ethoxymethylene) bis (tricyclohexylphosphine), ruthenium, dichloro (ethoxymethylene) bis (tricyclopentylphosphine), ruthenium, dichloro (t-butylvinylidene) bis (tricyclohexylphosphine), ruthenium, dichloro (t-butylamino)

In one embodiment, L or L 'and A or A' may combine where M includes ruthenium or os, each L, L ', L "independently

Examples of ruthenium carbene complexes include vinylidene) bis (tricyclopentylphosphine), ruthenium, dichloro (phenylvinylidene) bis (tricyclo-exylphosphine), ruthenium, dichloro (phenylvinylidene) bis (tricyclopentylphosphine), ruthenium, [2 - (( 6-bismethylethyl) -4-nitrophenyl) imino-kN) methyl-4-nitrophenolate-kO)] chloro- (phenylmethylene) (tricyclohexylphosphine), ruthenium, [2 - (((2,6-bismethylethyl) -4- nitrophenyl) imino-kN) methyl-4-nitrophenolate-kO)] chloro- (phenylmethylene) (tricyclopentylphosphine), ruthenium, [2 - (((2,6-bismethylethyl) -4-nitrophenyl) imino-kN) methyl-4 -nitrophenolate-kO)] chloro- (3-methyl-2-butenylidene) (tricyclohexylphosphine), ruthenium, [2 - (((2,6-bismethylethyl) -4-nitrophenyl) imino-kN) methyl-4-nitrophenolate- kO)] chloro- (3-methyl-2-butenylidene) (tri-cyclopentylphosphine), ruthenium, [1,3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] [2 - (((2 , 6-bismei (eti!) - 4-niiroeni!) Imino-k ^

methylene), ruthenium, [1,3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] [2 - (((2,6-bismethylethyl) -4-nitrophenyl) imino-kN) methyl-4 -nitrophenolate-kO)] chloro- (3-methyl-2-butenylidene), ruthenium, dichloro [1,3-dihydro-1,3-bis- (2,4,6-trimethylphenyl) -2H-imidezol-2-one 2-ylidene] (phenylmethylene) (tricyclohexylphosphine), ruthenium, dichloro [1,3-dihydro-1,3-bis- (2,4,6-trimethylphenyl) -2H-imidazol-2-ylidene] (phenylmethylene) (tricyclopentyl)

ruthenium, dichloro [1,3-dihydro-1,3-bis- (2,4,6-trimethylphenyl) -2H-imidazol-2-ylidene] (3-methyl-2-butenylidene) (tricyclohexylphosphine), ruthenium, dichloro [1,3-Dihydro-1,3-bis- (2,4,6-trimethylphenyl) -2H-imidazol-2-ylidene] (3-methyl-2-butenylidene) (tricyclopenphosphine), ruthenium, dichloro [ 1,3-dihydro-1,3-bis- (2,4,6-trimethylphenyl) -2H-imidazol-2-ylidene] (3-phenyl-2-propenylidene) (tricyclohexylphosphine), ruthenium, dichloro [1,3 -dihydro-1,3-bis- (2,4,6-trimethylphenyl) -2H-imidazol-2-ylidene] (3-phenyl-2-ropenylidene) (tricyclopentylphosphine), ruthenium, dichloro [1,3- dihydro-1,3-bis- (2,4,6-trimethylphenyl) -2H-imidazole-2-ylidene] (ethoxymethylene) (tricyclohexylphosphine), ruthenium, dichloro [1,3-dihydro-1,3-bis - (2,4,6-trimethylphenyl) -2H-imidazol-2-ylidene] (ethoxymethylene) (tricyclopenphosphine), ruthenium, dichloro [1,3-dihydro-1,3-bis- (2,4,6 -trimethylphenyl) -2H-imidazol-2-ylidene] (t-butylvinylidene) (tricyclohexylphosphine), ruthenium, dichloro [1,3-dihydro-1,3-bis- (2,4,6-trimethylphenyl) -2H-imidazole -2-ylidene] (t-butylvinylidene) (tricyclopentylphosphine) ruthenium, dichloro [1,3-dihydro-1,3-bis- (2,4,6-trimethylphenyl) -2H-imidazol-2-ylidene] (phenylvinylidene) (tricyclohexylphosphine), ruthenium, dichloro [1,3-dihydro] -1,3-bis- (2,4,6-trimethylphenyl) -2H-imidazol-2-ylidene] (phenylvinylidene) (tricyclopentylphosphruthenium, [1,3-bis- (2,4,6-trimethylphenyl)) -2-imidazolidinylidene] dichloro (phenylmethylene) (tri-cyclohexylphosphine), ruthenium, [1,3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] -dichloro (phenylmethylene) (tricyclopentylphosphine), ruthenium, dichloro [1,3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] (3-methyl-2-butenylidene) (tricyclohexylphosphine), ruthenium, dichloro [1,3-bis- (2,4, 6-trimethylphenyl) -2-imidazolidinylidene] (3-methyl-2-butenylidene) (tricyclopentylphosphine), ruthenium, dichloro [1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene] (3-phenyl -2-propylidene) (tricyclohexylphosphine), ruthenium, dichloro- [1,3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] (3-phenyl-2-propylidene) (tricyclopentylphosphine), ruthenium, [1,3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] - dichloro (ethoxymethylene) (tricyclolyhexylphosphine)} ruthenium, [1,3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (ethoxymethylene) (tricyclopentylphosphine), ruthenium, [1,3-bis- ( 2,4,6-trimethylphenii) -2-imidazoyl-1-ylidene] -diorior (t-butylviniexylphosphine), ruthenium, [1,3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] -dichloro- (t- butylvinylidene) (tricyclopentylphosphine), ruthenium, [1,3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (phenylvinylidene) (tricycloexylphosphine), and ruthenium [1,3-bis- (2) 4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (phenylvinylidene) (tricyclopentylphosphine).

Commercially available Ru-based metathesis catalysts include ruthenium, dichloro (phenylmethylene) bis (tricyclohexylphosphine) (sometimes referred to as First Generation Grubbs Catalyst), ruthenium, [1,3-bis- (2, 4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (phenylmethylene) (tricyclohexylphosphine) (sometimes referred to as Second Generation Grubbs Catalyst), ruthenium, dichloro [[2- (1-methylethyloxy) phenyl] methylene] (tricyclohexylphosphine) ), (sometimes referred to as First Generation Hoveyda-Grubbs Catalyst), and ruthenium, [1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro [[2, (1 methylethyloxy) phenyl] methylene] (sometimes referred to as Second Generation Hoveyda-Grubbs Catalyst). These Ru-based metathesis catalysts are available from Materia Inc. (Pasadena, California).

In one embodiment, the Ru-based or Os-based metathesis catalyst may be prepared in situ. For example, a Ru or Os compound may be combined with alkyne and an appropriate ligand under known conditions to form a carbene-metal complex, such as those described above.

Other metathesis catalysts that are also useful include tungsten and / or molybdenum metathesis catalysts. Such catalysts include those which may be formed in situ from salts such as tungsten salts, and molybdenum and tungsten complexes known as Schrock carbenes. Additionally, sustained systems may be used, especially when fasegas polymerization is employed. Tungsten metathesis catalysts are further described in U.S. Patent Nos. 3,932,373, and 4,391,737, and Schrock catalysts are described in U.S. 4,681,956,5,087,710, and 5,142,073, all of which are incorporated herein by reference.

3. Monomer

In one or more embodiments, useful olefin monomers include those that will undergo the metathesis reaction, i.e. those that include at least one metathesically active double bond. The cycloolefines may be cycloalkene or cyclopolyene. Suitable examples of acyclic monomers include dienes, alpha omega dienes, olefin oligomers, and the like.

In certain embodiments, the olefin is a mixture of two or more different olefins which differ in at least one respect, such as the number of carbon atoms or heteroatoms and the substituent amount and type. Two or more different olefins may also refer to two or more olefin isomers. In one embodiment, the ratio of the first olefin to the second olefin is about 99: 1 to 1:99, in another mode, from about 95: 5 to 5:95, and in another embodiment, about 90. : 10 to 10:90. In this case, when ROMP is used, the cyclolefin includes a mixture of two or more cycloolefins that differ in ring size or substituents, or a mixture of two or more decycloolefin isomers. Any combination of two or more cycloolefins may be used to provide the desired polymeric properties as discussed below. In one embodiment, the mixture includes cyclooctadiene and cyclopentene, or in other embodiments 1,5-cyclooctadiene and cyclooctene.

Any cycloolefin that may participate in a ring opening metathesis (ROMP) polymerization reaction may be used. Acycloolefin may include one or more substituent groups and / or functional groups. Cyclolefin may be a cycloalkene or a cyclopolyene.

Cycloolefins include the compounds represented by the formula

<formula> formula see original document page 12 </formula>

where z includes an integer from 1 to about 18. Exemplary decycloolefins include cyclopropene, cyclobutene, benzocyclobutene, cyclopenthene, dicyclopentadiene, norbornene, norbornadiene, cycloheptene, 7-oxanorbornene, 7-oxanorbornadiene, cyclodecene, 1, 3-cyclooctadiene, 1,5-cyclooctadiene, 1,3-cycloheptadiene, [2.2.1] bicycloeptenes, [2.2.2] bicyclooctenes, cyclohexenylnorbornenes, dicarboxylic anhydrides denorbornen, cyclododecene, 1,5,9-cyclododecatriene and derivatives thereof. It will be appreciated by those skilled in the art that ring-opening polymerization thermodynamics vary based on factors such as ring size and substituents. Ring opening metathesis is described in K.J. Ivinand J.C. Mol, Olefin Methatesis and Methatesis Polymerization, Chap. 11 (1997), which is incorporated herein by reference.

An alkene that includes a functional group must be present. Functional alkene, which may also be referred to as a functionalizing agent, includes at least one metathesically active double bond. Alkenocyclic includes functional terminal groups. Alkene can be represented by the formula

<formula> formula see original document page 12 </formula>

where Z includes a functional group and η includes an integer from 0 to about 20. A mixture of two or more functionalized alphaolefins may be used.

In one embodiment, the acyclic functional alkene may be represented by the formula <formula> formula see original document page 13 </formula>

where each Ζ, which may be the same or different, is a functional group and η is an integer from 0 to about 20, in another embodiment, η is an integer from about 1 to about 9, yet another mode, η is an integer less than about 6.

5. Summary

The synthetic techniques employed to prepare the unsaturated metathesis polymers with at least one or more terminal functional groups employed in the present invention include conventional metathesis polymerization techniques. Such reactions may include ring-opening polymerization via ROM (ROMP) and / or acyclic diene metastasis polymerization (ADMET); Such reactions are known in the art as disclosed in U.S. Patent Nos. 5,728,917 and 5,290,895, and 5,969,170, which are incorporated herein by reference. Metathesis polymers can also be prepared by depolymerization via metathesis of higher molecular weight unsaturated polymers (see WO 06/06/127483 A1). The use of functional alkenes, which include multifunctional alkenes, in metathesis reaction, is also known as described in Patent No. 2. No. 5,880,231 and No. 2. Serial No. 11 / 344,660, which are incorporated herein by reference.

In one or more embodiments, reagents and catalysts are introduced into an inert atmosphere. The order of reagent addition or catalyst addition is not particularly limited. In one embodiment, the functional alkene and one or more metathesis-active olefins are combined to form a mixture, and then the metathesis catalyst is added to the mixture, m or more of these materials may be introduced together with a mixture. solvent. In other embodiments, the monomer or demonomer mixtures may be first polymerized followed by the addition of functionalized alkene.

Metathesis polymerization reactions typically occur at temperatures that are below the ceiling temperature of one or more monomers. Ceiling temperature is the temperature above which polymerization does not occur to a remarkable extent. In one embodiment, metathesis sandblasting occurs at a temperature of from below 40 ° C to about 100 ° C, in another embodiment, the temperature is from about 20 ° C to about 75 ° C, in yet another embodiment, the temperature is about 0Ca at about 55 ° C.

Reaction progress can be optionally monitored by standard analytical techniques, or by monitoring the percentage of solids. The metathesis reaction may optionally be completed by adding a catalyst deactivator such as vinyl ethyl ether.

After the reaction, the metathesis polymerized polymer may be isolated from the solvent using conventional procedures. In one or more embodiments, especially where functional groups are water sensitive, known techniques may be used to prevent or reduce contact with water.

When a monomer mixture is employed, the relative amount of each monomer is not particularly limited. In one embodiment, the ratio of the first monomer to the second monomer is from about 99: 1 to about 1:99, in another embodiment, the ratio of the first monomer to the second monomer is from about 95: 5 to about 5. : 95, in yet another embodiment, the ratio of the first monomer to the second monomer is from about 90:10 to about 10:90.

The amount of metathesis catalyst employed in the metathesis reaction is not important, however, the catalytic amount of catalyst is typically employed. In one embodiment, the amount of catalyst is at least about 0.1 mmol catalyst per 100 mo olefin, in other embodiments at least about 1 mmol catalyst per 100 mo olefin, in other embodiments, the amount of catalyst is from about 5 mmol to about 10 mo of catalyst per 100 mo of olefin, and still other embodiments, from about 10 mmol to about 1 mol decatalyst per 100 mo of olefin, and yet another embodiment. about 0.02a to about 0.5 mol of catalyst per 100 mo olefin. In other embodiments, the metathesis catalysts may be employed in conjunction with existing high molecular weight metathesis polymers to form the desired polymers of this invention. . In other words, metathesis catalysts may be employed to prepare the polymer of a desired molecular weight by introducing the catalyst into the high molecular weight and alkene polymer. The high pesomolecular polymer that can be used in this process includes a molecular high molecular weight polymer produced by metathesis polymerization. For example, the high molecular weight polymer from cyclooctenoque polymerization has a molecular weight of about 90 kg / moi, less than 1% pendant vinyl, and about 12 to 15 double bonds per 100 carbonone atoms polymer chain. are commercially available under the tradename Vestenamer® (Degussa). Such polymers may contact a metathesis catalyst and an alkene to produce a lower molecular weight demetathesis polymer. Also, by employing functionalized alkenes, the resulting metathesis polymer can be functionalized. Optionally, a cycloolefin or diene containing a metathesis reactive double bond may be added for copolymerization with the base polymer and thereby form an interpolymer.

6. Characteristics of Unsaturated Polymer

The. Group Content Pending Vinila

In one or more embodiments, the unsaturated metathesis polymer having at least one or more terminal functional groups employed in the present invention may be characterized by a relatively low vinyl pendant group content. The pendant vinyl group refers to an alkenyl group along the polymer backbone with a backbone attachment point without including a terminal group. In one or more embodiments, the polymer may include less than about 2%, in other embodiments, less than about 1%, in other embodiments, less than about 0.5%, and in other embodiments, less than about 2%. 0.05% vinyl or setting groups 1,2. In one or more embodiments, the unsaturated polymer is substantially devoid of pending vinyl units wherein substantially devoid of that amount includes or fewer vinyl pendant units that could otherwise have a noticeable impact on the polymer and / or blend. of the invention. In one or more embodiments, the unsaturated polymer is devoid of pendant vinyl groups.

B. Glass Transition Temperature (Tg)

In one or more embodiments, the Tg of the demetathesis unsaturated polymer having at least one or more terminal functional groups may be less than about 0 ° C, in other embodiments, less than about 10 ° C, and still in other embodiments. less than about minus 15 ° C. In yet another embodiment, the Tg may be from less than 15 to minus 115 ° C.

ç. Fusion Temperature (Tm)

In one or more embodiments, the melting point of the unsaturated polymer having at least one or more terminal functional groups may be from about minus (-) 40 ° C to about (+) 50 ° C, in other embodiments. about minus 35 ° C to about 40 ° C, and in still other ways from about minus 30 ° C to about 20 ° C.

In certain embodiments, when the polymer backbone is synthesized from two or more different monomers, the melting point of the polymer may be controlled by selecting the relative amounts of monomers. For example, the melting point of a copolymer prepared from cyclooctadiene and cyclopentene may range from about minus (-) 30 ° C to about (+) 40 ° C since the mol fraction of pen units The content of the copolymer decreases from about 0.3 to about zero percent based on the total cyclooctadiene and cyclopentene levels.

d. Average Molecular Weight (Mn)

In one or more embodiments, the unsaturated polymer having at least one or more terminal functional groups may be characterized by an average molecular weight (Mn) of at least about 0.5 kg / mol, in other embodiments at least about 1 kg / mol. mol, in other embodiments, at least about 1.5 kg / mol, and in other embodiments, at least about 2.0 kg / mol. In one or more embodiments, the unsaturated polymer may be characterized by an average molecular weight of less than about 100 kg / mol, in other embodiments less than about 80 kg / mol, in other embodiments less than about 60 kg / mol, and in other embodiments less than 40 kg / mol and in another embodiment less than about 20 kg / mol. In one or more embodiments, the unsaturated polymer may be characterized by a molecular weight distribution (Mw / Mn) of from about 1.05 to about 2.5, in other embodiments from about 1.1 to about 2.0, and in other embodiments, from about 1.2 to about 1.8. Molecular weight can be determined using standard GPC techniques with polystyrene standards.

f. Dual Binding Content

In one or more embodiments, the metathesis polymer having at least one or more terminal functional groups may be characterized by relatively low unsaturation. In one or more embodiments, the metathesis opolymer contains from about 5 to about 25 double bonds per 100 carbon atoms, in other embodiments, the metathesis polymer contains from about 6 to about 20 double bonds per 100 carbon atoms. in other embodiments, from about 7 to about 18 double bonds per 100 carbon atoms, and in other embodiments, the metathesis polymer contains from about 10 to about 15 double bonds per 100 carbon atoms in the polymer.

q. Microstructure

The metathesis polymers of the present invention have a wtether of about 10%; and in another mode, more than 30%, and in another mode, more than 50%.

D. Mixture / Reaction Polymer and PET

1. General

In one or more embodiments of this invention, the compositions may be prepared by mixing or combining an aromatic polyester resin and the metathesis polymer having at least one or more terminal functional groups herein. Techniques for mixing are known, and this invention is not limited to selecting a particular method. In one embodiment, mixing occurs in a reactive extruder, such as a twin-screw former extruder.

2. Conditions

Mixing or combining the aromatic polyester resin and metathesis dopolymer having at least one or more terminal functional groups can occur over a wide range of conditions. These conditions are selected so that substantially all functional groups attached to the metathesis polymer react with poly (ethylene terephthalate). In one or more embodiments, the mixing or combination may occur at a temperature of from about 230 ° C to about 310 ° C and, in other embodiments, from about 250 ° C to about 290 ° C.

3. Length of Stay

In one or more embodiments, the residence time within the extruder is maintained for about 2 to about 6 minutes, and in other embodiments from about 3 to about 5 minutes.

4. Other Ingredients

In one or more embodiments, the aromatic polyester resin and metathesis polymer having at least one or more terminal functional groups may be mixed or combined in the presence of catalysts, modifiers, heat stabilizers, antioxidants, dyes, crystallizing nucleating agents, fillers, biodegradation accelerators or additional constituents that may be incorporated into the composition. In general, aromatic polyester compositions are known as descriptone U.S. Patent No. 6,083,585, which is incorporated herein by reference.

In one or more embodiments, the aromatic polyester composition may include a transition metal catalyst.

In one or more embodiments, the aromatic polyester compositions of this invention include from about 0.05 to about 0.15 weight percent of transition metal catalyst based on the weight of the metathesis polymer. In other embodiments, the composition includes from about 0.07 to about 0.12 weight percent, and in other embodiments, from about 0.09 to about 0.11 weight percent based on the weight of the metathesis polymer .

In one or more embodiments, the α-aromatic polyester compositions may include or may be modified by condensation or coupling branching agents which alter the intrinsic viscosity of the compositions. In other words, the compositions include the reaction product between the branching agent and the aromatic polyester and / or metathesis polymer having at least one or more terminal functional groups. Such agents may include polycondense branching agents. In one or more embodiments, such branching agents may include trimellitic anhydride, aliphatic dianhydrides, aromatic dianhydrides. In one embodiment, pyromellitic dianhydride (i.e. 1,2,4,5-tetracarboxylic acid dianhydrides) is employed.

Numerous factors may alter the amount of ramification agent that may be desirable, or alter the possibility that a darification agent may be desired. In one or more embodiments, the composition of this invention includes or is modified from about 0.01 to about 0.15 weight percent branching agent based on the weight of the metathesis polymer. In other embodiments, the composition includes from about 0.05 to about 0.12 weight percent, and in other embodiments, from about 0.09 to about 0.11 weight percent of a basogenous branching agent. of the metathesis polymer having at least one or more terminal functional groups herein.

5. Quantities

The. Focused

In one or more embodiments of this invention, the composition comprising the aromatic polyester resin and the metathesis polymer which has at least one or more terminal functional groups herein are prepared as concentrates or masterbatches which may subsequently be added to other compounds. thermoformed resins (eg aromatic polyester resins) for use in the preparation of particulate articles. In forming such concentrates, which are generally in the form of pellets, the composition of this invention may include at least 1%, in other embodiments, at least 5%, and in other embodiments, at least 10% by weight of metathesis unsaturated polymer having at least 1%. at least one or more terminal functional groups herein based on the total weight of the total composition. In such and other embodiments, such masterbatch concentrates or pellets include less than 30%, and in other embodiments, less than 20%, and in other embodiments, less than 15% by weight of the metathesis polymer based on the total weight of the composition.

B. Thermoformed Composition

In one or more embodiments of this invention, particularly when the composition is employed in the thermoforming process (as opposed to the manufacture of main batch concentrate or pellets), the compositions include at least 0.05%, in other embodiments at least 0.5%, and in other embodiments. other embodiments, at least 0.9% by weight of the metathesis polymer based on the total weight of the composition. In these and other embodiments, the thermoformed composition includes less than 5%, in other embodiments less than 3%, and in other embodiments less than 1.5% by weight based on the total weight of the composition.

In one or more embodiments, the composition of the invention includes reaction product between an aromatic polyester resin and a metathesis polymer having at least one or more terminal functional groups herein.

E. Morphology

In one or more embodiments, the compositions of this invention include an aromatic polyester resin matrix which has dispersed therein domains of the metathesis polymer. According to those skilled in the art, the characteristics, especially size, of these metathesis polymer domains may be adjusted based on the mixing conditions and functionality of the metathesis polymer. In one or more modalities, the metathesis polymer domains are expected to be characterized by an expected average diameter of less than 400 nanometers, in other modalities less than 300 nanometers expected, and in other modalities less than 200 nanometers expected. The size and stability of the formed domains is expected to be controlled and stabilized by the plating and attachment of the functional metathesis polymer to the aromatic polyester.

F. Uses

In one or more embodiments, the compositions of this invention are advantageously thermoformed, and therefore they may be used in various known thermoforming techniques, such as, but not limited to, injection molding, blow molding, compression molding. In one or more embodiments, the compositions of this invention may also be extruded.

In one or more embodiments, the compositions may be used to manufacture packaging walls and packaging articles. In certain embodiments, such packaging items include those used in perishable foods and beverages.

In a particular use, the compositions of this invention may be used to make bottles. In other embodiments, the compositions may be used in the manufacture of packaging films.

G. Advantages

Compositions of one or more embodiments of this invention are advantageously recyclable where color formation is reduced. An additional disadvantage can be expected by the reaction and attachment of the functional metathesis polymer to the aromatic polyester substantially reducing the disruption or migration of the rubber polymer away from the polyester.

To demonstrate the practice of the present invention, the following examples were prepared and tested. The examples should not, however, be considered as limiting the scope of the invention. The claims will serve to define the invention.

Example 1

Synthesis of low pesomolecular telequelic acetate terminated polypentenomer

A batch mixture comprising 1.51 kg of nitrogen-purified cyclopentene and 0.087 kg of 1,4-diacetoxy-2-butene was charged to a 3.78 l volume reactor heated to 25 ° C. , and stirred. A solution of 0.4 g of 2-generation Grubbs metathesis catalyst [Aldrich] in 100 mL of degassed, dry toluene (0.45 mmol, 50,000: 1olefin: Ru) was charged to the vessel. Within 25 minutes, polymerization of the monomer began to occur, and an increase in reaction temperature to 78 ° C was observed. The resulting cement was then stirred at a constant temperature of 40 ° C for an additional hour. At this time, a solution of 5 mL of ethyl vinyl ether in 50 mL of toluene was added to the polymer solution and stirred at 40 ° C to deactivate any residual metathesis catalyst. The resulting polymer had the following characteristics: Mn = 6.3 kg / mol; Mw / Mn = 1.8; trans olefin content = 78%; devinyl olefin content = 0%; > 95% acetate-terminated end groups. Hydrolysis of ester end groups to hydroxyl end groups in polypentenomer.

A 250 g solution of acetonated terminated polypentamer prepared above dissolved in 1.5 L of toluene was stirred and cooled to 0 ° C in an ice bath. Approximately 500 mL of 0.5 M sodium methoxide in methanol solution was added to the polymer solution and stirred for 4 hours at 0 ° C. At this time, the polymer solution was poured into a flask containing 1 L of 0.5 M HCl methanolic solution and stirred for 30 minutes. The resulting mixture was placed in a separatory funnel and allowed to separate two layers. The lower wet methanol layer was removed and the polymer was extracted with 1 L of 1L water aliquots until the pH of the solution was neutral. Any emulsions formed were separated by the addition of saturated NaCl solution. After extraction, the polymer solution was dried using anhydrous magnesium sulfate and the solvent removed under reduced pressure. 1 H NMR analysis indicated that 98% of the acetate end groups were hydrolyzed to hydroxyl groups.

The resulting hydroxyl-terminated polypentamer is expected to be useful in preparing compositions with aromatic polyesters.

Synthesis of low molecular weight tele-cyclic cycloocteno-1,5-cyclooctadiene copolymer In a 3.78 l volume stainless steel reactor, a batch mixture was charged consisting of 1185 mL (996 g, 9.0 mo) of degassed cyclooctene, 560 mL (497 g, 4.6 mo) of degassed 1,5-cyclooctadiene, and 60 mL (65.5 g, 0.38 mol) of degassed cis-1,4-diacetoxy-2-butene. The mixture was stirred and heated to 50 ° C. A solution of 0.42 g (0.50 mmol) of 2-generation Grubbs deruthenium metathesis catalyst in 10 mL of dry toluene and degassed prepared under atmospheric conditions. inert and added to the monomeric mixture. Within 1 minute, an increase in reaction temperature began to occur, with the peak temperature reaching 114 ° C within 15 minutes. The reaction was stirred for two hours, after which a 10 mL solution of vinyl ethyl ether in hexanes was added to deactivate the metathesis catalyst. After stirring for 30 minutes, the polymer was added to bottles for storage and analyzed. The product polymer was a yellowish-brown oily liquid. The resulting material had the following characteristics: Mn = 9.2 kg / mol; Mw / Mn = 1.82; 67/33 trans / cisolefin content; 48/52 molar ratio of octenyl / butenyl units.

Example 3

Depolymerization of high molecular weight polyoctenamer to low molecular weight telecellic cycloocteno-1,5-cyclooctadiene copolymer. In a 3.78 l stainless steel reactor, 830 g of polyoctenamer feet (Degussa Vestenamer 8012) (Mn = 65 kg / mol; Mw / Mn = 1.8; 100% octenyl unit composition) ), 470 mL (417 g, 3.85 mo) of degassed 1,5-cyclooctadiene, 40 mL (43.4 g, 0.25 mol) decas-1,4-diacetoxy-2-butene, and 700 mL degassed hexanes were charged. The heterogeneous mixture was stirred and heated to 57 ° C to melt the solid Vestenamer polymer. A solution of 0.22 g (0.26 mmol) of 2-generation Grubbs ruthenium-based catalyst in 10 mL of dried and degassed toluene was prepared under an atmospheric container and added to the reactor contents. The reaction was stirred for two hours at a constant temperature of 57 ° C. After this time, a solution of 5 ml of vinyl ethyl ether in 100 ml of hexanes was added to deactivate the metathesis catalyst. After stirring for 30 minutes, the polymer was added to storage bottles and analyzed.

The polymer of the product was a yellowish-brown oily liquid. The resulting material had the following characteristics: Mn = 7.4 kg / mol; Mw / Mn = 2.09; 48/52 molar ratio of octenyl / butenyl units.

According to the polymer of Example 1, the terminal functionalized polymers of Examples 2 and 3 are expected to be useful in preparing compositions with aromatic polyesters.

Various modifications and alterations that do not deviate from the scope and spirit of this invention will become obvious to those skilled in the art. This invention should not be limited to the illustrative embodiments herein.

Claims (19)

A composition comprising: (i) an aromatic polyester; and (ii) an unsaturated polymer formed via metathesis polymerization which has at least one or more terminal functional groups selected from the group consisting of hydroxyl groups, carboxylic acid, ester, carbonate, cyclic carbonate, anhydride, cyclic anhydride , lactone, amine, amine, lactam, cyclic ether, ether, aldehyde, thiazoline, oxazoline, phenol, melamine and such mixtures. The composition of claim 1, wherein the aromatic dithopolyester comprises a poly (alkylene terephthalate) resin. A composition according to claim 2, wherein the poly (alkylene terephthalate) ditaresine is selected from the group consisting of empoly (ethylene terephthalate), poly (butylene terephthalate), mixtures thereof, and interpolymers thereof. The composition of claim 1, wherein the unsaturated metathesis polymer comprises from about 5 to about 25 double bonds per 100 carbon atoms in the polymer. The composition of claim 1, wherein the terminal functional group is selected from the group consisting of hydroxyl, ester and carboxylic acid groups and mixtures thereof. A composition according to claim 1 comprising at least about 0.5 wt% unsaturated metathesis polymer based on the total weight of the unsaturated metathesis polymer and aromatic depolyester resin. The composition of claim 1, wherein the unsaturated metathesis dithopolymer has less than about 2% pendant vinyl groups. A composition according to claim 1 further comprising a cobalt compound. A reaction product comprising: (i) an aromatic polyester; and (N) an unsaturated polymer formed by metathesis polymerization having at least one or more terminal functional groups selected from the group consisting of hydroxyl groups, carboxylic acid, ester, carbonate, cyclic carbonate, anhydride, cyclic anhydride, lactone, amine, amine, lactam, cyclic ether, ether, aldehyde, thiazoline, oxazoline, phenol, melamine and such mixtures. The composition of claim 9, wherein the aromatic dithiopolyester comprises a poly (alkylene terephthalate) resin. The composition according to claim 10, wherein the poly (alkoxy terephthalate) resin is added is selected from the group consisting of poly (ethylene terephthalate), poly (butylene terephthalate), mixtures thereof and interpolymers thereof. The composition of claim 9, wherein the unsaturated metathesis dithopolymer comprises less than about 2% pendant vinyl groups. A composition according to claim 9, wherein the unsaturated metathesis polymer comprises from about 5 to about 25 double bonds per 100 carbon atoms in the polymer. A composition according to claim 9, wherein the terminal functional group is selected from the group consisting of hydroxyl, ester and carboxylic acid groups and mixtures thereof. The composition of claim 9, wherein the aromatic dithopolyester and said unsaturated metathesis polymer are covalently bonded to each other by an ester bond. A composition according to claim 9 comprising at least about 0.5% by weight of unsaturated metathesis polymer based on the total weight of the unsaturated metathesis polymer and aromatic polyester resin. A composition according to claim 9 further comprising a cobalt compound. A composition according to claim 10 further comprising a coupling agent. The composition of claim 1, wherein the unsaturated metathesis dithopolymer has an average molecular weight (Mn) of from about 1 to about 100 kg / mol.